KR20220112277A - Silirane functionalized compounds, especially organosilicon compounds for the preparation of siloxanes - Google Patents

Abstract

The present invention describes silirane functionalized compounds consisting of a substrate to which two or more silirane groups of formula (I) are covalently bonded, mixtures comprising the silirane functionalized compounds according to the present invention, and processes for the preparation of siloxanes .

Description

Silirane compounds as stable silylene precursors and their use in the catalyst-free preparation of siloxanes

The present invention describes silirane functionalized compounds consisting of a substrate to which two or more silirane groups of formula ( I ) are covalently bonded, as well as mixtures comprising the silirane functionalized compounds of the present invention, and processes for the preparation of siloxanes do. Crosslinking occurs through thermal activation of polyfunctional silylenes that represent stable precursors to highly reactive silylene species. Network formation here is achieved via the reaction of silylene with functionalized siloxanes or polysiloxanes, allowing the use of a broad spectrum of common siloxane compounds.

Prior art and technical purpose

Silicon is of great interest due to its excellent chemical and physical properties, and thus has been used in various ways. In contrast to the situation in carbon-based plastics, the van der Waals forces between homopolymer chains are very weak in the case of siloxanes. In siloxane homopolymers this leads to flow behavior and very poor properties even at very high molecular weights. For this reason, the siloxane is crosslinked and thus obtains a rubbery elastic state.

Several known methods exist for crosslinking siloxanes, and a fundamental distinction is made between addition crosslinking, condensation crosslinking, and radical crosslinking. In the case of addition crosslinking, vinyl functionalized siloxanes are reacted with hydridosiloxanes without removal products in a process called hydrosilylation (RTV-2 or HTV). The reaction requires the use of a non-recoverable noble metal catalyst (usually platinum). In the case of condensation crosslinking, the terminal silanol groups react with other silicon functional groups (eg Si-O-CH ₃ , Si-OC ₂ H ₅ , Si-O-COCH ₃ ). The reaction is accompanied by removal of small, volatile compounds such as acetic acid or alcohols, and thus also physical shrinkage. The condensation crosslinking system can be operated as a one-component system activated by contact with a small amount of water (RTV-1). The mixture is usually mixed with a metal catalyst (eg, tin-based) to accelerate the crosslinking reaction. In the case of radical crosslinking, organic peroxides that decompose into radicals upon heating are used (HTV). Reactive radicals crosslink, for example, vinyl methyl siloxane.

While the high reactivity in the processes mentioned is induced by catalysts, the crosslinking method described herein is based on the particularly high reactivity of silylene. Silylene is an uncharged divalent silicon compound and is therefore a heavier homologue of carbene. Because of their variable reactivity, silylene compounds are suitable for crosslinking a wide variety of monomers. For example, silylene reacts with Si-H compounds in an insertion reaction to form disilane. Reaction with nucleophiles such as silanols or alcohols is likewise accomplished via insertion into an O-H bond. Insertion of silylene into the Si-O bond of the alkoxy silane forms the disilane. Together with alkenes and alkynes, silylene enters a cycloaddition reaction to form silacyclopropane (silirane) or silacyclopropene (silylene), respectively.

Scheme 1: Reactivity of the silylene compound. Silylenes are intercalated or reacted with double bonds in, for example, Si-H-, Si-OH- and Si-OR- compounds in cycloaddition reactions.

There are several known methods for the synthesis of silylene. Decomposition of polysilanes by UV light or heat yields, for example, highly reactive silylenes such as Me ₂ Si:, which are not stable and rapidly dimerize. Since polysilane is produced under very harsh conditions, this synthesis method leaves little room for functional group selection. More complex silylenes are available through reduction of dihalosilanes. The reducing agent used may be, for example, lithium or KC ₈ . There are known silylene compounds with thermodynamic and kinetic stabilizing groups that are reliably stable at room temperature. Therefore, highly stabilized silylenes are less suitable as functional groups for bonding siloxanes because the reactivity decreases as the stability of silylenes increases. Expensive and inconvenient stabilization with complex ligands can also be too costly and inconvenient in industrial quantities. Thus, for the siloxane bonding methods described herein, a precursor rather than silylene is used, and the precursor can be converted to silylene by external influences. Particularly suitable for this purpose are silirane compounds, which can be cleaved, for example, by appropriate activation, pyrolysis or photolysis, into silylenes and olefins. The driving force for dissociation is the high ring tension of silirane. Silirane compounds are much more stable than their silylene analogues and can be considered as masked silylenes. The stability, or required decomposition temperature, of the silirane can be controlled by its functionalization. Silirane may further react with nucleophilic compounds such as alcohols, for example in ring opening reactions. Since this is an addition reaction, there are no removal products in this case. Therefore, the use of silanane in the bonding of siloxanes allows compatibility with a very broad spectrum of functional groups. Siliranes are generally very reactive due to the high ring tension of the cyclic structure.

Scheme 2: Reaction behavior of silylane and silylene. Silirane can be cleaved by pyrolysis or photolysis to form olefins and silylenes.

In the literature [Macromolecules 2003 , 36 , 1474-1479], it has been shown that monofunctional silanes can be anionic polymerized.

References (a) [Russian Journal of Applied Chemistry 2002 , 75 (1) , 127-134], (b) [Russian Chemical Reviews 2011 , 80 (4) , 3313-339], and (c) [Applied Organometallic Chemistry 1990 ] , 4 , 163-172, Semenov et al. describe oligodimethylsilane as a source of photochemically generated silylene for crosslinking of silanol terminated vinylmethylsiloxanes. Crosslinking occurs by the formation of silanane with highly reactive silylene and vinyl groups, which can then react with silanol groups. The silylane formed is not detected during crosslinking, and therefore the correctness of the mechanism is questionable. Also, due to the low UV transmittance, this method is only possible with very small film thicknesses (~100 μm film).

In addition, the following bifunctional bis-silirane compounds are known from Journal of Organometallic Chemistry 2011 , 696 , 1957-1963:

.

.

Scheme 3: bifunctional bis-silylane by Fink et al.

It is also known from WO2015/088901 that monosilirane can be used for the surface functionalization of substrates terminated with OH groups, NH ₂ groups or NH groups.

Stabilized bis-silylene (cf. Scheme 4) is likewise known from the literature (Angew. Chem. Int Ed. 2009 , 48 , 8536-8538 and J. Am. Chem. Soc. 2010 , 132 , 15890-15892), although , their use in the polymer chemistry sector is not described.

Scheme 4: Stabilized bis-silylene known from the literature

Only US2002/0042489A1 discloses the use of heterocyclic silylenes as catalysts for the polymerization of alkenes or alkynes.

technical achievement

A subject of the present invention is a silirane functionalized compound consisting of a substrate to which two or more silirane groups of the formula ( I ) are covalently bonded:

the index n in the above formula ( I ) takes a value of 0 or 1;

the radical R ^a is a divalent C ₁ -C ₂₀ hydrocarbon radical;

The radical R ¹ is

(i) a C ₁ -C ₂₀ hydrocarbon radical,

(ii) a C ₁ -C ₂₀ hydrocarbonoxy radical,

(iii) silyl radicals - SiR ^a R ^b R ^c , wherein the radicals R ^a , R ^b , R ^c independently of one another are C ₁ -C ₆ hydrocarbon radicals,

(iv) amine radicals - NR ^x ₂ , wherein the radicals R ^x are independently of one another

(iv.i) hydrogen,

(iv.ii) a C ₁ -C ₂₀ hydrocarbon radical, and

(iv.iii) silyl radicals - SiR ^a R ^b R ^c , wherein the radicals R ^a , R ^b , R ^c independently of one another are C ₁ -C ₆ hydrocarbon radicals.

selected from the group consisting of), and

(v) imine radicals -N=CR ¹ R ² , wherein the radicals R ¹ , R ² are independently of each other

(v.i) hydrogen,

(v.ii) a C ₁ -C ₂₀ hydrocarbon radical and

(v.iii) silyl radicals —SiR ^a R ^b R ^c , wherein the radicals R ^a , R ^b , R ^c independently of one another are C ₁ -C ₆ hydrocarbon radicals

selected from the group consisting of)

is selected from the group consisting of;

The radicals R ² , R ³ , R ⁴ , R ⁵ are independently of each other selected from the group consisting of (i) hydrogen, (ii) halogen, and (iii) C ₁ -C ₂₀ hydrocarbon radicals, the radicals R ² and R ⁴ may be part of a cyclic radical.

The substrate is preferably selected from the group consisting of organosilicon compounds, hydrocarbons, silica, glass, sand, stone, metal, semimetal, metal oxide, mixed metal oxide, and carbon-based oligomers and polymers.

The substrate is more preferably composed of silanes, siloxanes, precipitated silica, fumed silica, glass, hydrocarbons, polyolefins, acrylates, polyacrylates, polyvinyl acetates, polyurethanes and polyethers composed of propylene oxide and/or ethylene oxide units. selected from the group.

One particular embodiment of the present invention is a silirane functionalized organosilicon compound of the general formula ( II ):

(SiO _4/2 ) _a (R ^x SiO _3/2 ) _b (R'SiO _3/2 ) _b' (R ^x ₂ SiO _2/2 ) _c (R ^x R'SiO _2/2 ) _c'

(R' ₂ SiO _2/2 ) _c'' (R ^x ₃ SiO _1/2 ) _d (R'R ^x ₂ SiO _1/2 ) _d' (R' ₂ R ^x SiO _1/2 ) _d''

(R' ₃ SiO _1/2 ) _d''' (II);

In the above general formula, the radicals R ^x are independently of each other (i) hydrogen, (ii) halogen, (iii) unsubstituted or substituted C ₁ -C ₂₀ hydrocarbon radical and (iv) unsubstituted or substituted C ₁ -C ₂₀ hydro selected from the group consisting of a carbonoxy radical;

The indices a , b , b' , c, c', c'', d, d', d'', d''' represent the number of each siloxane unit of the compound and are independently of each other integers ranging from 0 to 100,000; , provided that the sum of a, b, b', c, c', c'', d, d', d'', d''' takes a value of 2 or more, and among the exponents b' , c', d ' at least one is at least 2 or at least one of the exponents c'', d'' or d''' is non-zero;

The radical R' is a silirane group of the formula ( IIa ):

In the above formula, the exponent n takes a value of 0 or 1;

the radical R ^a is a divalent C ₁ -C ₂₀ hydrocarbon radical;

The radical R ¹ is

(i) a C ₁ -C ₂₀ hydrocarbon radical,

(ii) a C ₁ -C ₂₀ hydrocarbonoxy radical,

(iii) silyl radicals - SiR ^a R ^b R ^c , wherein the radicals R ^a , R ^b , R ^c independently of one another are C ₁ -C ₆ hydrocarbon radicals,

(iv) amine radicals - NR ^x ₂ , wherein the radicals R ^x are independently of one another

(iv.i) hydrogen,

(iv.ii) a C ₁ -C ₆ hydrocarbon radical, and

(iv.iii) silyl radicals - SiR ^a R ^b R ^c , wherein the radicals R ^a , R ^b , R ^c independently of one another are C ₁ -C ₆ hydrocarbon radicals.

selected from the group consisting of), and

(v) imine radicals -N=CR ¹ R ² , wherein the radicals R ¹ , R ² are independently of each other

(v.i) hydrogen,

(v.ii) a C ₁ -C ₂₀ hydrocarbon radical and

(v.iii) silyl radicals - SiR ^a R ^b R ^c , wherein the radicals R ^a , R ^b , R ^c independently of one another are C ₁ -C ₆ hydrocarbon radicals.

selected from the group consisting of)

is selected from the group consisting of;

The radicals R ² , R ³ , R ⁴ , R ⁵ are independently of each other selected from the group consisting of (i) hydrogen, (ii) halogen, and (iii) C ₁ -C ₂₀ hydrocarbon radicals, the radicals R ² and R ⁴ may be part of a cyclic radical.

The arrangement of the silicon atoms of a silirane functionalized compound is of fundamental importance. It is absolutely necessary for the silicon atoms to be interconnected through the core scaffold. In this way, after activation of the silylene functionalized compound, a crosslinkable compound having a plurality of silylene groups is obtained. When the silicon atoms are not bridged with each other, activation of the sililane results in free "monosilylene" and polyfunctional vinyl compounds. This free monosilylene cannot crosslink and reacts with the functional groups of the siloxane (compare scheme 6).

The radical R ^a in the formula ( IIa ) is preferably a C ₁ -C ₃ alkylene radical. More preferably the radical R ^a is an ethylene radical.

By means of the substituents R ¹ on the silicon atom of silirane, through kinetic and thermodynamic control, the reactivity and stability of the silirane functionalized compound can be affected. The radical R ¹ in the formula ( IIa ) is preferably (i) a C ₁ -C ₆ hydrocarbon radical and (ii) an amine radical - N(SiR ^a R ^b R ^c ) ₂ , wherein the radicals R ^a , R ^b , R ^c is, independently of each other, a C ₁ -C ₆ hydrocarbon radical). The radical R ¹ in formula ( IIa ) is more preferably selected from the group consisting of (i) C ₁ -C ₆ alkyl radicals and (ii) - N(SiMe ₃ ) ₂ .

The radicals R ² , R ³ , R ⁴ , R ⁵ in the formula ( IIa ) are, independently of each other, preferably selected from the group consisting of (i) hydrogen and (ii) C ₁ -C ₆ alkyl radicals, the radicals R ² and R ⁴ may be part of a cyclic radical. The radicals R ² , R ³ , R ⁴ , R ⁵ in the formula ( IIa ) are independently of each other more preferably selected from the group consisting of (i) hydrogen and (ii) C ₁ -C ₆ alkyl radicals, the radicals R ² and R ⁴ may be part of a hexenyl radical.

One preferred embodiment is a silirane functionalized compound, wherein in formula ( II ) the indices a , b , b' , c, c', c'', d, d'' and d''' are 0 takes the value of and the exponent d' takes the value of 2; The index n in formula ( IIa ) takes a value of 1; the radical R ^a is a C ₁ -C ₃ alkylene radical; The radicals R ¹ are (i) a C ₁ -C ₆ hydrocarbon radical and (ii) an amine radical - N(SiR ^a R ^b R ^c ) ₂ , wherein the radicals R ^a , R ^b , R ^c independently of one another are C ₁ - is a C ₆ hydrocarbon radical; The radicals R ² , R ³ , R ⁴ , R ⁵ are independently of each other selected from the group consisting of (i) hydrogen and (ii) C ₁ -C ₆ alkyl radicals, the radicals R ² and R ⁴ being part of a cyclic radical may be

Another preferred embodiment is a silirane functionalized compound, wherein in formula ( II ) the indices a , b , b' , c, c', c'', d, d'' and d''' are zero. takes a value and the exponent d' takes a value of 2; The index n in formula ( IIa ) takes a value of 1; the radical R ^a is an ethylene radical; the radical R ¹ is selected from the group consisting of (i) a C ₁ -C ₆ alkyl radical and (ii) - N(SiMe ₃ ) ₂ ; The radicals R ² , R ³ , R ⁴ , R ⁵ are independently of each other selected from the group consisting of (i) hydrogen and (ii) C ₁ -C ₆ alkyl radicals, wherein the radicals R ² and R ⁴ are part of a hexenyl radical may be

Particularly preferred examples of silirane functionalized compounds of the present invention are the compounds SV1 , SV2 and SV3 shown in Scheme 5 below.

Scheme 5: Particularly Preferred Silirane Functionalized Compounds

Silirane functionalized organosilicon compounds are synthesized, for example, by reduction of dihalosilane with a reducing agent such as lithium or potassium graphite in a polar coordination solvent (eg, tetrahydrofuran). Reduction of the dihalosilane group forms the intermediate silylene, which is removed as an olefin compound and reacts to form silylene.

As the olefin compound for removing silylene, generally any compound having a double bond can be used. Since the substituents on the silirane ring have a decisive effect on reactivity, the choice of olefin may be used to influence the behavior of the silirane functionalized organosilicon compound. During activation of the silylene functionalized organosilicon compound, the silylane is again cleaved into silylene and olefins. It is therefore advantageous to select olefinic compounds which are gaseous and volatilizable under the reaction conditions of the conversion reaction.

Alternatively, silirane functionalized compounds may be prepared via Wurtz coupling in which a C-C bond of the silirane ring is formed.

Another subject of the present invention is

a) at least one silirane functionalized compound of the present invention; and

b) at least one compound A having in each case at least two radicals R'

Including, wherein the radicals R' are independently of each other

(i) -Si-H ,

(ii) -OH ,

(iii) -C _x H _2x -OH , wherein x is an integer ranging from 1 to 20;

(iv) -C _x H _2x -NH ₂ , wherein x is an integer ranging from 1 to 20;

(v) - SH , and

(vi) - R ^a _n -CR=CR ₂ , wherein R ^a is a divalent C ₁ -C ₂₀ hydrocarbon radical and the index n takes on the value 0 or 1 and the radicals R independently of one another (vi.i) hydrogen and (vi.ii) selected from the group consisting of C ₁ -C ₆ hydrocarbon radicals)

It is a mixture selected from the group consisting of.

One particular embodiment of the present invention is a mixture wherein compound A is selected from functionalized siloxanes of the general formula ( III ):

(SiO _4/2 ) _a (R ^x SiO _3/2 ) _b (R'SiO _3/2 ) _b' (R ^x ₂ SiO _2/2 ) _c (R ^x R'SiO _2/2 ) _c'

(R' ₂ SiO _2/2 ) _c'' (R ^x ₃ SiO _1/2 ) _d (R'R ^x ₂ SiO _1/2 ) _d' (R' ₂ R ^x SiO _1/2 ) _d''

(R' ₃ SiO _1/2 ) _d''' (III),

The radicals R ^x in the above general formula are independently of each other selected from the group consisting of (i) halogen, and (ii) unsubstituted or substituted C ₁ -C ₂₀ hydrocarbon radicals;

The radicals R' are independently of each other

(i) hydrogen;

(ii) -OH ,

(iii) -C _x H _2x -OH , wherein x is an integer ranging from 1 to 20;

(iv) -C _x H _2x -NH ₂ , wherein x is an integer ranging from 1 to 20;

(v) - SH , and

(vi) - R ^a _n -CR=CR ₂ , wherein R ^a is a divalent C ₁ -C ₂₀ hydrocarbon radical and the index n takes the value 0 or 1 and the radicals R are, independently of one another, (i) hydrogen and (ii) selected from the group consisting of C ₁ -C ₆ hydrocarbon radicals)

is selected from the group consisting of;

The indices a , b , b' , c, c', c'', d, d', d'', d''' represent the number of each siloxane unit of the compound and are independently of each other integers ranging from 0 to 100,000; , provided that the sum of a, b, b', c, c', c'', d, d', d'', d''' takes a value of 2 or more, and among the exponents b' , c', d ' at least one is greater than or equal to 2 or at least one of the exponents c'', d'' or d''' is non-zero.

The silirane functionalized compounds of the present invention are stable precursors of highly reactive silylenes. Silylene groups are formed from each silylene group only after activation of the crosslinking agent. Therefore, the silirane functionalized compounds of the present invention must have at least two silirane groups in order to be able to function as a crosslinking agent.

Scheme 6: Schematic comparison of two different bis-silane structures. Top: Silicon atoms of the silirane functionalized compound bridged through the structural scaffold generate crosslinkable reactive bis-silylene species upon activation. Bottom: Sililane groups that are not bridged via silicon atoms decompose into non-crosslinked cleavage products upon activation.

Another subject of the present invention is

(i) according to certain embodiments, providing a mixture according to the invention, and

(ii) reacting the mixture by thermal activation, photochemical activation or catalytic activation;

It is a method for producing a siloxane comprising a.

The linking of the mixture of functionalized siloxanes of formula ( III ) and the linking of the silirane functionalized compounds of the present invention can be achieved via thermal activation, photochemical activation or catalytic activation. In the linking procedure, the silirane units of the organosilicon compound react to form silylene, which then reacts and crosslinks with the functional groups of the siloxane.

There are a variety of ways in which the silirane functionalized compounds of the present invention can be activated (ie, silirane is converted to silylene). Thermal activation requires a temperature higher than the decomposition temperature of the silirane compound. Silirane compounds can also be converted to silirane by photochemical activation. The wavelengths required for this purpose are in the UV range. The reactivity of silirane is the same for both activation methods. In addition, catalysts may be used to accelerate the linking reaction or catalysts may be used for room temperature crosslinking. Suitable catalysts are compounds that destabilize the silylenes leading to cleavage into silylenes and olefins. Examples of such catalysts are AgOTf and Cu(OTf) ₂ . In general, activation of silirane also yields olefinic compounds (eg, 2-butene).

Due to their high reactivity, activated silirane functionalized compounds can react with a broad spectrum of functional groups. Possible reaction partners are, for example, Si-H, Si-OR, Si-OH, C-OH, -NH ₂ , SH and -vinyl. As a result, all common functional groups of industrial siloxanes are supported. Functionalized siloxanes must have at least two specified functional groups to form a network. The mechanism of crosslinking of the bifunctional siloxane with the silylene compound is that each insertion of the formed silylene forms a new group that can be attacked to form a nodal point.

Other functional groups on the (poly)siloxane (eg, Si-OH end of the chain, methylvinyl group) are also possible. Due to differences in reactivity (ring addition), vinyl substituted (poly)siloxanes must have at least 3 vinyl groups.

The properties of the crosslinked polymer can be altered through the length and/or molecular mass of the functionalized siloxane. The silylene bonding method can be performed with functionalized siloxanes of low molecular mass and functionalized siloxanes of high molecular mass. Examples of functionalized siloxane compounds are shown in Scheme 7 below.

Scheme 7: Examples of functionalized siloxanes that can be used for reaction with silirane functionalized compounds of the present invention

The reaction of the functional groups of the silylene with the siloxane is accomplished by inserting the silylene into the functional group. Reaction of silylene with hydridosiloxanes and alkoxysiloxanes produces a disilane bond between the silylene functionalized compound and the siloxane. These disilanes have newly formed Si-H or Si-OR groups, which represent an additional point of attack for silylene. Thus, each reaction of silylene with siloxane produces additional attachable functional groups. Nucleophilic functional groups such as silanols, alcohols and amines are likewise reacted with silylene via insertion of silylene into the functional group. In this case no disilane is formed; Instead, siloxanes and silazanes are formed, which also have newly formed Si—H functional groups for further crosslinking. Through the formation of novel attachment points during the reaction, siloxanes with only two functionalities are also available.

Scheme 8: Overview of possible crosslinking strategies for forming siloxane networks with hydridosiloxanes (left), siloxanols (center) and vinylsiloxanes (right).

For the preparation of the siloxane, the functionalized siloxane of formula ( III ) is mixed with the silirane functionalized compound of the present invention until homogeneous mixing is ensured. Linking occurs only through activation of the mixture by one of the three methods above. The mixture is activated until the silirane functionalized compound of the present invention is completely consumed by the reaction, or until the desired properties are achieved. A successful crosslinking procedure is likewise possible. For air-sensitive silanic functionalized compounds, inert gas or other suitable measures should be used to prevent contact with oxygen and water.

The reaction temperature is selected to be higher than the decomposition temperature of the silylene functionalized compound, which is the formation of silylene by pyrolysis. Typically the temperature is in the range of 60 to 200 °C, preferably in the range of 80 to 150 °C, more preferably in the range of 130 to 150 °C.

The silirane functionalized compound is mixed with the functionalized siloxane of formula ( III ) in an appropriate molar ratio. Typically the molar ratio of silirane groups to functional groups in the siloxane ranges from 4:1 to 1:4, preferably from 1:1 to 1:4.

Example

All syntheses were performed in a baked glass apparatus under Schlenk conditions. Argon or nitrogen was used as an inert gas. Chemicals used (vinylsilane, vinylsiloxane, silicone oil, etc.) were obtained from WACKER Chemie AG, ABCR or Sigma-Aldrich. Cis-2-butene (2.0) and trans-2-butene (2.0) were obtained from Linde AG. All solvents were dried and distilled before use. All silicone oils were dried and degassed over Al ₂ O ₃ and 3 Å molecular sieves prior to use. Molecular weights are expressed as average values and are based on the manufacturer's figures. The polysiloxane used is a random copolymer. All chemicals used were stored under inert gas. Elemental lithium (Sigma-Aldrich, 99%, trace metal based) and sodium (Sigma-Aldrich, 99.8%, sodium based) were melted at 200° C. in a nickel crucible under an argon atmosphere to obtain lithium having a sodium fraction of 2.5%. The Li/Na alloy was cut into very small pieces prior to use to increase the surface area. Al ₂ O ₃ (neutral) and activated carbon were dried under high vacuum at 150° C. for 72 hours.

Magnetic resonance spectroscopy ( ¹ H, ²⁹ Si) was performed using a Bruker Avance III 500 MHz.

Mass spectrometry analysis was performed using a LIFDI-MS 700 with an ion source from Linden CMS.

Elemental analysis was performed using Elementar's Vario EL in the microanalysis laboratory of the chemistry department of Munich Technical University.

Synthesis Example 1: 1,3-bis (2- (1- ( tert -Butyl)-2,3-dimethylsiliran-1-yl)ethyl)-1,1,3,3-tetramethyldisiloxane ( SV1 ) manufacturing

Starting from the starting compound divinyltetramethyldisiloxane, bis-silirane ( SV1 ) was synthesized through a three-step reaction route. In the first synthesis step, this compound was reacted with trichlorosilane via hydrosilylation in the presence of a Karstedt catalyst (platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex). reacted. For this reaction, 100 g (740 mmol, 4.0 equiv) of trichlorosilane was introduced into 30 mL of toluene in a 250 mL Schlenk flask and mixed with 34.4 g (180 mmol, 1.0 equiv) of divinyltetramethyldisiloxane. did. Then 0.05 mL of Karstedt catalyst (2.1-2.4% Pt in xylene) was added to the reaction mixture, which was stirred at room temperature for 18 hours. After completion of the reaction, the mixture was filtered through dried neutral aluminum oxide, and the residual solvent was removed under reduced pressure. This gave 81.3 g (96%, 177 mmol) of the product (Cl ₃ SiCH ₂ CH ₂ SiMe ₂ ) ₂ O as a clear colorless liquid.

¹ H-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = 0.10 (s, 12 H, CH ₃ ), 0.55-0.60 (m, 4 H, CH ₂ ), 1.05-1.10 (m, 4 H, CH ₂ ).

²⁹ Si-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = 8.14 (SiO), 13.84 (SiCl ₃ ).

EA [%]: Calculation: C　=　21.01, H　=　4.41, Actual measurement: C　=　20.93, H　=　4.63

The following synthetic steps were performed by substituting tert -butyllithium for hexachlorosilane. For this reaction, 30.0 g (65.6 mmol, 1.0 equiv) of (Cl ₃ SiCH ₂ CH ₂ SiMe ₂ ) ₂ O was dissolved in 75 mL of pentane and the solution was cooled to -10°C. 8.40 g (131 mmol, 2.0 equiv) 1.7 M tert-butyllithium solution was slowly added dropwise via a dropping funnel. The reaction was then heated to 0° C. and stirred for 8 h. The formed lithium chloride was removed by filtration, and the filtrate was separated from the solvent under reduced pressure. Sublimation of the crude product under high vacuum (110° C., 10 ⁻⁵ mbar) gave 22.0 g (67%, 43.9 mmol) of tetrachlorosilane (Cl ₂ t BuSiCH ₂ CH ₂ SiMe ₂ ) ₂ O as a white solid. .

¹ H-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = 0.05 (s, 12 H, Si-CH ₃ ), 0.78-0.82 (m, 4 H, CH ₂ ), 1.00 (s, 18 H, SiC-CH ₃ ), 1.04-1.08 (m, 4 H, CH ₂ ).

²⁹ Si-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = 8.22 (Si-O), 38.47 (Si- t BuCl ₂ ).

EA [%]: Calculation: C　=　38.39, H　=　7.65, Actual measurement: C　=　38.25, H　=　7.76

The last step in the synthesis of bis-silirane involves the reduction of tetrachlorosilane by means of a lithium-sodium alloy (2.5% Na). For this reaction step, 10.0 g (20.0 mmol, 1.0 equiv) of tetrachlorosilane (Cl ₂ tBu SiCH ₂ CH ₂ SiMe ₂ ) ₂ O was dissolved in 50 mL of THF. The reaction solution was cooled to -30°C, after which 33.6 g (600 mmol, 30.0 equiv) of cis-butene were incorporated by condensation. 2.10 g (300 mmol, 15.0 equiv) of lithium-sodium alloy (2.5% Na) were added in countercurrent argon and the reaction solution was stirred vigorously at room temperature for 7 days. When the reduction of chlorosilane was complete, the solvent was removed under reduced pressure and the residue was absorbed in pentane. The precipitated lithium salt was removed by filtration, and the filtrate was dried again under reduced pressure. This gave 7.80 g (86%, 16.7 mmol) of bis-silirane ( SV1 ) as a yellow oil. Due to the purity of the cis-butene gas used (purity 2.0), trans and 1-butene species were found along with the cis species.

Trans Species:

¹ H-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = 0.12-0.14 (m, 12 H, Si-CH ₃ ), 0.46-0.52 (m, 4 H, Si CH ₂ ), 0.74- 0.78 (m, 4 H, Si-CH ₂ ), 1.12 (s, 18 H, SiC-CH ₃ ), (m, 4 H, Si-CH), 1.43-1.45 (m, 12 H, SiCH-CH ₃ ) ).

²⁹ Si-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = -53.11 (CH-Si-CH), 8.01 (Si-O).

cis species:

¹ H-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = 0.14-0.16 (m, 12 H, Si-CH ₃ ), 0.86-0.88 (m, 8 H, CH ₂ ), 1.03 (s) , 18 H, SiC-CH ₃ ), 1.08-1.11 (m, 4 H, Si-CH), 1.43-1.45 (m, 12 H, SiCH-CH ₃ ).

²⁹ Si-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = -49.70 (CH-Si-CH), 7.30 (Si-O).

1-butene species:

¹ H-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = 0.07-0.10 (m, 12 H, Si-CH ₃ ), 0.59-0.68 (m, 4 H, Si-CH ₂ ), 0.79 -0.81 (m, 4 H, Si-CH ₂ ), 1.08 (s, 18 H, SiC-CH ₃ ), 1.18-1.19 (m, 2 H, CH ₂ Si-CH-CH ₂ CH ₃ ), 1.19- 1.20 (m, 4 H, CHSi-CH ₂ ), 1.39-1.40 (m, 4 H, SiCH-CH ₂ -CH ₃ ), 1.47-1.49 (m, 6 H, SiCHCH ₂ -CH ₃ ).

²⁹ Si-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = -42.34 (CH ₂ -Si-CH), 6.89 (Si-O).

EA [%]: Calculation: C　=　61.20, H　=　11.56, Actual measurement: C　=　58.13, H　=　11.31

LIFDI-MS: (THF) m/z = 471.95 [M] ⁺ , 415.99 [MC ₄ H ₈ ] ⁺ , 360.01 [MC ₈ H ₁₆ ] ⁺ .

The three specified bis-silicones have the same molecular mass because they are stereoisomers. Therefore, they cannot be distinguished in the mass spectrum. The same is true for elemental analysis results.

Synthesis Example 2: 1,3-bis(2-(7-(tert-butyl)-7-silabicyclo[4.1.0]heptan-7-yl)ethyl)-1,1,3,3-tetramethyl disiloxane ( SV2 ) manufacturing

Tetrachlorosilane (Cl ₂ tBuSiCH ₂ CH ₂ SiMe ₂ ) ₂ O representing the starting compound of this synthesis was prepared by a route similar to that of Synthesis Example 1. For subsequent reduction, 1.00 g (2.00 mmol, 1.0 equiv) of tetrachlorosilane was mixed with 3.94 g (47.9 mmol, 24.0 equiv) of cyclohexene in 2.5 mL of THF. The reaction solution was mixed with 208 mg (29.9 mmol, 25.0 equiv) of a lithium-sodium alloy (2.5% Na) and stirred vigorously at room temperature for 10 hours. When the reduction of all chlorosilanes was complete, the solvent and excess cyclohexene were removed under reduced pressure, and the residue was resuspended in 5 mL of pentane. The precipitated LiCl was removed and the filtrate was dried under reduced pressure. This gave 382 mg (37%, 0.73 mmol) of bis-silirane ( SV2 ) as a clear oil. Cis and trans species of bis-silirane ( SV2 ) were obtained.

cis species:

¹ H-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = 0.13-0.15 (m, 12 H, Si-CH ₃ ), 0.90 (m, 8 H, Si-CH ₂ ), 1.03 (s) , 18 H, SiC-CH ₃ ), 1.49-1.54 (m, 8 H, SiCHCH ₂ —CH ₂ ), 1.71-1.78 (m, 8 H, SiCH-CH ₂ ), 1.98-2.05 (m, 4 H, Si-CH).

²⁹ Si-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = -49.09 (Si-CH), 7.27 (Si-O).

Trans Species:

¹ H-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = 0.12-0.13 (m, 12 H, Si-CH ₃ ), 0.47-0.52 (m, 4 H, Si-CH ₂ ), 0.77 -0.81 (m, 4 H, Si-CH ₂ ), 1.15 (s, 18 H, SiC-CH ₃ ), 1.64-1.67 (m, 4 H, Si-CH), 1.78-1.83 (m, 8 H, SiCHCH ₂ -CH ₂ ), 1.88-1.97 (m, 8 H, SiCH-CH ₂ ).

²⁹ Si-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = -53.75 (Si-CH), 7.89 (Si-O).

Synthesis Example 3: 1,3-bis (2- (7- ( tert -Butyl)-7-silabicyclo[4.1.0]heptan-7-yl)ethyl)-1,1,3,3-tetramethyldisiloxane ( SV3 ) manufacturing

Bis-silane ( SV3 ) was prepared from the corresponding hexachlorosilane via two-step synthesis. In the first step 10.0 g (21.9 mmol, 1.0 equiv) of (Cl ₃ SiCH ₂ CH ₂ SiMe ₂ ) ₂ O was introduced into 40 mL of THF and cooled to 0°C. A solution of 8.72 g (43.7 mmol, 2.0 equiv) of potassium-hexamethyldisilazane (KHMDS) in 30 ml of THF was then slowly added dropwise over a period of 30 minutes. The resulting suspension was stirred at room temperature for 6 hours. The solvent was then removed under reduced pressure. The residue was dissolved in 40 mL of pentane and then filtered. The solvent was removed again under reduced pressure to obtain 12.5 g (81%, 17.7 mmol) of (TMS ₂ NCl ₂ SiCH ₂ CH ₂ SiMe ₂ ) ₂ O as a clear yellow liquid.

¹ H-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = 0.07 (s, 12 H, OSi-CH ₃ ), 0.33 (s, 36 H, NSi-CH ₃ ), 0.83-0.87 (m , 4 H, OSi-CH ₂ ), 1.25-1.29 (m, 4 H, NSi-CH ₂ ).

²⁹ Si-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = 2.19 (Si-Cl ₂ ), 6.38 (Si-Me ₃ ), 8.45 (Si-O).

EA [%]: Calculation: C　=　33.97, H　=　07.98, N　=　03.96, Actual measurement: C　= 33.39, H　=　07.96, N　=　03.94

The next reaction step involves reduction of the tetrachlorosilane to give the corresponding bis-silane. For this reaction, 10.0 g (14.2 mmol, 1.0 equiv) of (TMS ₂ NCl ₂ SiCH ₂ CH ₂ SiMe ₂ ) ₂ O was dissolved in 50 mL of THF and the reaction mixture was conditioned to -30°C. Then 23.10 g (424 mmol, 30.0 equiv) of cis-butene were introduced into the reaction vessel by condensation and 1.47 g (212 mmol, 15.0 equiv) of a lithium-sodium alloy (2.5% Na) was added countercurrent to argon. The reaction mixture was warmed to room temperature and stirred for 5 days. After complete reduction of chlorosilane, the solvent was removed under reduced pressure and the residue was resuspended in 30 mL of pentane. The precipitated lithium chloride was isolated and the product solution was filtered through dry neutral aluminum oxide. The filtrate was then dried under reduced pressure to give 5.46 g (57%, 8.06 mmol) of a cis/trans mixture as a yellow turbid oil and also the corresponding bis-silane from the 1-butene species ( SV3 ).

cis species:

¹ H-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = 0.12-0.13 (m, 12 H, OSi-CH ₃ ), 0.22 (s, 36 H, NSiCH ₃ ), 0.77-0.80 (m) , 8 H, CH ₂ ), 1.12-1.15 (m, 4 H, Si-CH), 1.19-1.21 (m, 12 H, CH-CH ₃ ).

²⁹ Si-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = -50.01 (CH-Si-CH), 4.71 (N-Si-TMS), 7.81 (Si-O).

Trans Species:

¹ H-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = 0.11-0.12 (m, 12 H, Si-CH ₃ ), 0.25-0.26 (m, 36 H, NSiCH ₃ ), 0.47-0.52 (m, 4 H, CH ₂ ), 0.81-0.85 (m, 4 H, CH ₂ ), 1.17-1.18 (m, 4 H, Si-CH), 1.27-1.30 (m, 12 H, CH-CH ₃ ) ).

²⁹ Si-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = -44.90 (CH-Si-CH), 4.70 (N-Si-TMS), 7.68 (Si-O).

1-butene species:

¹ H-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = 0.09-0.10 (m, 12 H, Si-CH ₃ ), 0.23-0.24 (m, 36 H, NSiCH ₃ ), 0.52-0.57 (m, 4 H, SiCH ₂ ), 0.67-0.71 (m, 4 H, SiCH ₂ ), 0.93-0.99 (m, 4 H, SiCH-CH ₂ ), 1.27 (m, 2 H, CH ₂ Si-CH ), 1.34-1.35 (m, 6 H, SiCHCH ₂ -CH ₃ ).

²⁹ Si-NMR: (294 K, 500 MHz, C ₆ D ₆ ) δ = -41.12 (CH-Si-CH), 5.31 (N-Si-TMS), 7.86 (Si-O).

EA [%]: Calculation: C　=　49.63, H　=　10.71, N　=　4.13, Actual measurement: C　=　47.34, H　=　10.60, N　=　3.98

LIFDI-MS: (THF) m/z= 675.69 [M] ⁺ , 619.75 [MC ₄ H ₈ ] ⁺ , 564.25 [MC ₈ H ₁₆ ] ⁺ , 244.06 [MC ₂₀ H ₅₂ N ₂ Si ₄ ] ⁺ .

Use Example 1: hydridomethylsiloxane-dimethylsiloxane copolymer and SV1 crosslinking of

SV1 (100 mg, 212.3 μmol, 1.0 eq) and silicone oil (254 mg, 106.2 μmol, 0.5 eq, 2.395 g/mol, (25-30% methylhydridosiloxane-dimethylsiloxane copolymer, Si-H terminus)) was weighed into a suitable vessel under inert gas at a molar ratio of 1:2 (silirane groups to Si-H groups). The mixture was dissolved in 0.5 mL of pentane and stirred with a magnetic stir bar until homogeneous mixing was ensured. The pentane was then removed again under reduced pressure. Crosslinking occurred at 140° C. for 24 h under inert gas. The product was a slightly cloudy, colorless, non-tacky, slightly elastic polymer. Due to the short chain length of the siloxane, the material is quite brittle and ruptures under tensile loading. The polymer swells greatly in benzene and does not dissolve. There were no soluble components detectable by NMR spectroscopy. Butenes formed from cross-linking can be detected through their characteristic odor.

Use Example 2: hydridomethylsiloxane-dimethylsiloxane copolymer and SV3 crosslinking of

SV3 (100 mg, 147.6 μmol, 1.0 equiv) and silicone oil (233 mg, 97.4 µmol, 0.66 equiv, 2.395 g/mol, (25-30% methylhydridosiloxane-dimethylsiloxane copolymer, Si-H terminus)) was weighed into a suitable container under inert gas at a molar ratio of 1:3 (silirane groups to Si-H groups). The mixture was stirred with a magnetic stir bar until homogeneous mixing was ensured. Crosslinking occurred at 140° C. for 24 h under inert gas. The product was a clear, slightly yellow, non-tacky, slightly elastic polymer. Due to the short chain length of the siloxane, the material is quite brittle and ruptures under tensile loading. The polymer swells greatly in benzene and does not dissolve. There were no soluble components detectable by NMR spectroscopy.

Use example 3: hydridomethylsiloxane-dimethylsiloxane copolymer and SV3 crosslinking of

SV3 (100 mg, 147.6 μmol, 1.0 equiv) and silicone oil (78 mg, 32.5 µmol, 0.22 equiv, 2.395 g/mol, (25-30% methylhydridosiloxane-dimethylsiloxane copolymer, Si-H terminus)) was weighed into a suitable vessel under inert gas at a molar ratio of 9:10 (silirane groups to Si-H groups). The mixture was stirred with a magnetic stir bar until homogeneous mixing was ensured. Crosslinking occurred at 140° C. for 24 h under inert gas. The product was a clear, slightly yellow, non-tacky, slightly elastic polymer. Due to the short chain length of the siloxane, the material is quite hard and brittle and ruptures under tensile loading. The polymer swells greatly in benzene and does not dissolve. There were no soluble components detectable by NMR spectroscopy. Due to the high silanane fraction, the polymer is much harder than in Use Example 2.

Use Example 4: hydridomethylsiloxane-dimethylsiloxane copolymer and SV3 crosslinking without inert gas of

SV3 (100 mg, 147.6 μmol, 1.0 equiv) and silicone oil (78 mg, 32.5 µmol, 0.22 equiv, 2.395 g/mol, (25-30% methylhydridosiloxane-dimethylsiloxane copolymer, Si-H terminus)) was weighed into a suitable vessel under inert gas at a molar ratio of 9:10 (silirane groups to Si-H groups). The mixture was stirred with a magnetic stir bar in air until homogeneous mixing was ensured. Crosslinking occurred at 140° C. for 24 h in air. The product was a clear, slightly yellow, non-tacky, slightly elastic polymer. This material exhibited properties similar to those of the elastomer described in Use Example 3. Oxygen and moisture in the ambient air had no discernible effect on the crosslinking of the polymer. Thus, bis-silirane ( SV3 ) is sufficiently stable with respect to air.

Use Example 5: hydridomethylsiloxane-dimethylsiloxane copolymer and SV1 crosslinking of

Inert SV1 (87.5 mg, 185.6 μmol, 10.0 equiv) and silicone oil (1.03 g, 18.58 µmol, 1.0 equiv, 55.000 g/mol, (0.5-1% methylhydridosiloxane-dimethylsiloxane copolymer, TMS terminus)). Weigh into a suitable container under gas at a molar ratio of 20:6 (silirane groups to Si-H groups). The mixture was stirred with a magnetic stir bar until homogeneous mixing was ensured. Crosslinking occurred at 140° C. for 24 h under inert gas. The product was a white, opaque, non-tacky elastomeric polymer. The polymer swells greatly in benzene and does not dissolve. There were no soluble components detectable by NMR spectroscopy.

Use Example 6: 2,4,6,8-tetramethylcyclotetrasiloxane (TMCTS) and SV1 crosslinking of

SV1 (100 mg, 212.3 μmol, 1.0 equiv) and cyclic siloxane TMCTS (23 mg, 95.53 µmol, 0.45 equiv, 2,4,6,8-tetramethylcyclotetrasiloxane) in a molar ratio of 1:0.9 ( Silirane groups to Si-H groups) were weighed into an appropriate container. The mixture was stirred with a magnetic stir bar until homogeneous mixing was ensured. Crosslinking occurred at 140° C. for 24 h under inert gas in a closed system. The product formed is a hard, transparent polymer, non-tacky and has some elastic properties. The polymer swells greatly in benzene and does not dissolve. There were no soluble components detectable by NMR spectroscopy.

Use Example 7: Short-chain OH-terminated polydimethylsiloxane and SV1 crosslinking of

SV1 (50 mg, 106.2 μmol, 1.0 equiv) and silicone oil (1.03 g, 106.2 µmol, 1.0 equiv, 9.750 g/mol, polydimethylsiloxane, OH terminus) were mixed under an inert gas in a molar ratio of 1:1 (silanic groups to Si-OH groups) into a suitable container. The mixture was stirred with a magnetic stir bar until homogeneous mixing was ensured. Crosslinking occurred at 140° C. for 24 h under inert gas. The polymer formed was colorless, slightly cloudy, non-tacky, and exhibited elastic properties.

Use Example 8: Short-chain OH-terminated polydimethylsiloxane and SV3 crosslinking of

SV3 (50 mg, 73.79 μmol, 1.0 equiv) and silicone oil (721 mg, 73.79 µmol, 1.0 equiv, 9.750 g/mol, polydimethylsiloxane, OH terminus) were mixed under an inert gas in a molar ratio of 1:1 (silanic groups to Si-OH groups) into a suitable container. The mixture was stirred with a magnetic stir bar until homogeneous mixing was ensured. Crosslinking occurred at 140° C. for 24 h under inert gas. The product formed is a colorless and slightly cloudy elastomeric polymer. The polymer swells greatly in benzene and does not dissolve. There were no soluble components detectable by NMR spectroscopy. Alternatively, a mixing molar ratio of 0.5:1 (silirane groups to Si-OH groups) and 2:1 (silirane groups to Si-OH groups) was used following a similar procedure. In the former case, a colorless, transparent, very soft and tacky elastomer was obtained. In the case of superstoichiometric addition of the crosslinking agent, a colorless turbid polymer with elastic properties was obtained. The resulting polymer was softer compared to the 1:1 mixture.

Use Example 9: Long-chain OH-terminated polydimethylsilane and SV1 crosslinking of

SV1 (34 mg, 73.8 μmol, 1.0 equiv) and silicone oil (67 mg, 73.8 µmol, 1.0 equiv, 36.000 g/mol, polydimethylsiloxane, OH terminus) were mixed under an inert gas in a molar ratio of 1:1 (silirane groups to Si-OH groups) into a suitable container. The mixture was stirred with a magnetic stir bar until homogeneous mixing was ensured. Crosslinking occurred at 140° C. for 24 h under inert gas. The product was a cloudy, soft elastomeric polymer. Due to the longer chain compared to Use Example 7, the polymer network was more flexible, providing a possible explanation for the lower strength of the formed elastomer. The polymer swells greatly in benzene and does not dissolve. There were no soluble components detectable by NMR spectroscopy.

Use Example 10: Long-chain OH-terminated polydimethylsilane and SV3 crosslinking of

SV3 (50 mg, 73.8 μmol, 1.0 equiv) and silicone oil (67 mg, 73.8 µmol, 1.0 equiv, 36.000 g/mol, polydimethylsiloxane, OH terminus) were mixed under an inert gas in a molar ratio of 1:1 (silirane groups to Si-OH groups) into a suitable container. The mixture was stirred with a magnetic stir bar until homogeneous mixing was ensured. Crosslinking occurred at 140° C. for 24 h under inert gas. The polymer formed was a clear, colorless, non-tacky elastomer. The addition of benzene greatly expands the polymer, but does not dissolve the polymer. There were no soluble components detectable by NMR spectroscopy.

Claims (12)

Silirane functionalized compounds consisting of a substrate to which two or more silirane groups of formula ( I ) are covalently bonded:

the index n in the above formula ( I ) takes a value of 0 or 1;
the radical R ^a is a divalent C ₁ -C ₂₀ hydrocarbon radical;
The radical R ¹ is
(i) a C ₁ -C ₂₀ hydrocarbon radical,
(ii) a C ₁ -C ₂₀ hydrocarbonoxy radical,
(iii) a silyl radical - SiR ^a R ^b R ^c , wherein the radicals R ^a , R ^b , R ^c are independently of each other selected from the group consisting of C ₁ -C ₆ hydrocarbon radicals;
(iv) amine radicals - NR ^x ₂ , wherein the radicals R ^x are independently of one another
(iv.i) hydrogen,
(iv.ii) a C ₁ -C ₂₀ hydrocarbon radical, and
(iv.iii) silyl radicals - SiR ^a R ^b R ^c , wherein the radicals R ^a , R ^b , R ^c independently of one another are C ₁ -C ₆ hydrocarbon radicals.
selected from the group consisting of), and
(v) imine radicals -N=CR ¹ R ² , wherein the radicals R ¹ , R ² are independently of each other
(vi) hydrogen;
(v.ii) a C ₁ -C ₂₀ hydrocarbon radical and
(v.iii) silyl radicals —SiR ^a R ^b R ^c , wherein the radicals R ^a , R ^b , R ^c independently of one another are C ₁ -C ₆ hydrocarbon radicals
selected from the group consisting of)
is selected from the group consisting of;
The radicals R ² , R ³ , R ⁴ , R ⁵ are independently of each other selected from the group consisting of (i) hydrogen, (ii) halogen, and (iii) C ₁ -C ₂₀ hydrocarbon radicals, the radicals R ² and R ⁴ may be part of a cyclic radical. The substrate of claim 1 , wherein the substrate is selected from the group consisting of organosilicon compounds, hydrocarbons, silica, glass, sand, stone, metal, semimetal, metal oxide, mixed metal oxide, and carbon-based oligomers and polymers. Silirane Functionalized Compounds. 3. A polyether according to claim 2, wherein the substrate is composed of silane, siloxane, precipitated silica, fumed silica, glass, hydrocarbon, polyolefin, acrylate, polyacrylate, polyvinyl acetate, polyurethane and propylene oxide and/or ethylene oxide units. Silirane functionalized compound, characterized in that selected from the group consisting of. According to claim 1, wherein the general formula (II) Silirane functionalized compound, characterized in that it is a silanic functionalized organosilicon compound selected from the group consisting of:
(SiO _4/2 ) _a (R ^x SiO _3/2 ) _b (R'SiO _3/2 ) _b' (R ^x ₂ SiO _2/2 ) _c (R ^x R'SiO _2/2 ) _c'
(R' ₂ SiO _2/2 ) _c'' (R ^x ₃ SiO _1/2 ) _d (R'R ^x ₂ SiO _1/2 ) _d' (R' ₂ R ^x SiO _1/2 ) _d''
(R' ₃ SiO _1/2 ) _d''' (II);
radicals in the above general formulaR ^x are independently of each other (i) hydrogen, (ii) halogen, (iii) unsubstituted or substituted C_One-C₂₀ hydrocarbon radicals and (iv) unsubstituted or substituted C_One-C₂₀ is selected from the group consisting of a hydrocarbonoxy radical;
Indicesa,b,b',c, c', c'', d, d', d'', d'''represents the number of each siloxane unit in the compound and independently of each other is an integer ranging from 0 to 100,000, provided thata, b, b', c, c', c'', d, d', d'', d'''The sum of takes a value greater than or equal to 2 and the exponentb',c', dat least one of ' is greater than or equal to 2 or an exponentc'', d'' ord''' at least one of them is non-zero;
radicalR'is the formula (IIa) is the siliran group of:

exponent in the above formulantakes a value of 0 or 1;
radicalR ^a is the divalent C_One-C₂₀ hydrocarbon radicals;
radicalR ^One silver
(i) C_One-C₂₀ hydrocarbon radicals,
(ii) C_One-C₂₀ hydrocarbonoxy radical,
(iii) silyl radicals- SiR ^a R ^b R ^c (here, radicalR ^a ,R ^b ,R ^c are independent of each other C_One-C₆ hydrocarbon radicals),
(iv) amine radicals- NR ^x ₂ (here, radicalR ^x are independent of each other
(iv.i) hydrogen,
(iv.ii) C_One-C₂₀ hydrocarbon radicals, and
(iv.iii) silyl radicals- SiR ^a R ^b R ^c (here, radicalR ^a ,R ^b ,R ^c are independent of each other C_One-C₆ hydrocarbon radicals)
selected from the group consisting of), and
(v) imine radicals-N=CR ^One R ² (here, radicalR ^One ,R ² are independent of each other
(v.i) hydrogen,
(v.ii) C_One-C₂₀ hydrocarbon radicals and
(v.iii) silyl radicals- SiR ^a R ^b R ^c (here, radicalR ^a ,R ^b ,R ^c are independent of each other C_One-C₆ hydrocarbon radicals)
selected from the group consisting of)
is selected from the group consisting of;
radicalR ² , R ³ , R ⁴ , R ⁵ are independently of each other (i) hydrogen, (ii) halogen, and (iii) C_One-C₂₀ selected from the group consisting of hydrocarbon radicals,R ² andR ⁴ may be part of a cyclic radical. 5. The method according to claim 4, wherein in formula ( II ) the indices a , b , b' , c, c', c'', d, d'' and d''' take the value 0 and the exponent d' of 2 takes a value; In the formula ( IIa ) the index n assumes a value of 1, the radical R ^a is a C ₁ -C ₃ alkenyl radical, the radical R ¹ is (i) a C ₁ -C ₆ hydrocarbon radical and (ii) an amine radical - N (SiR ^a R ^b R ^c ) ₂ , wherein the radicals R ^a , R ^b , R ^c independently of one another are C ₁ -C ₆ hydrocarbon radicals, the radicals R ² , R ³ , R ⁴ , R ⁵ are independently of each other selected from the group consisting of (i) hydrogen and (ii) C ₁ -C ₆ alkyl radicals, wherein the radicals R ² and R ⁴ may be part of a cyclic radical. compound. 6. A compound according to claim 5, wherein the radical R ^a in formula ( IIa ) is an ethylene radical; the radical R ¹ is selected from the group consisting of (i) a C ₁ -C ₆ alkyl radical and (ii) - N(SiMe ₃ ) ₂ ; The radicals R ² , R ³ , R ⁴ , R ⁵ are independently of each other selected from the group consisting of (i) hydrogen and (ii) C ₁ -C ₆ alkyl radicals, wherein the radicals R ² and R ⁴ are part of a hexenyl radical silanic functionalized compounds. 7. A silirane functionalized compound according to any one of claims 4 to 6 selected from the following compounds SV1 , SV2 and SV3 :

. a) at least one silirane functionalized compound as claimed in any one of claims 1 to 7; and
b) at least one compound A having in each case at least two radicals R'
Including, wherein the radicals R' are independently of each other
(i) -Si-H ,
(ii) -OH ,
(iii) -C _x H _2x -OH , wherein x is an integer ranging from 1 to 20;
(iv) -C _x H _2x -NH ₂ , wherein x is an integer ranging from 1 to 20;
(v) - SH , and
(vi) - R ^a _n -CR=CR ₂ , wherein R ^a is a divalent C ₁ -C ₂₀ hydrocarbon radical and the index n takes on the value 0 or 1 and the radicals R independently of one another (vi.i) hydrogen and (vi.ii) selected from the group consisting of C ₁ -C ₆ hydrocarbon radicals)
A mixture that is selected from the group consisting of. 9. The compound of claim 8Ato the general formula (III) of the functionalized siloxanes of:
(SiO _4/2 ) _a (R ^x SiO _3/2 ) _b (R'SiO _3/2 ) _b' (R ^x ₂ SiO _2/2 ) _c (R ^x R'SiO _2/2 ) _c'
(R' ₂ SiO _2/2 ) _c'' (R ^x ₃ SiO _1/2 ) _d (R'R ^x ₂ SiO _1/2 ) _d' (R' ₂ R ^x SiO _1/2 ) _d''
(R' ₃ SiO _1/2 ) _d''' (III),
radicals in the above general formulaR ^x are independently of each other (i) halogen, and (ii) unsubstituted or substituted C_One-C₂₀ selected from the group consisting of hydrocarbon radicals;
radicalR'are independent of each other
(i) hydrogen;
(ii)-OH,
(iii)-C _x H _2x -OH(here,xis an integer ranging from 1 to 20),
(iv)-C _x H _2x -NH ₂ (here,xis an integer ranging from 1 to 20),
(v)- SH, and
(vi)- R ^a _n -CR=CR ₂ (here,R ^a is the divalent C_One-C₂₀ Hydrocarbon radical and exponentntakes the value 0 or 1 and is a radicalRare independently of each other (vi.i) hydrogen and (vi.ii) C_One-C₆ selected from the group consisting of hydrocarbon radicals)
is selected from the group consisting of;
Indicesa,b,b',c, c', c'', d, d', d'', d'''represents the number of each siloxane unit in the compound and independently of each other is an integer ranging from 0 to 100,000, provided thata, b, b', c, c', c'', d, d', d'', d'''The sum of takes a value greater than or equal to 2 and the exponentb',c', dat least one of ' is greater than or equal to 2 or an exponentc'', d'' ord''' at least one of them is non-zero. (i) providing the mixture as claimed in claim 9, and
(ii) reacting the mixture by thermal activation, photochemical activation or catalytic activation;
A method for producing a siloxane comprising a. The method of claim 10 , wherein the activation occurs thermally and the temperature ranges from 60° C. to 200° C. 11 . 12. The process according to claim 10 or 11, wherein the molar ratio of silirane groups to functional groups in the siloxane ranges from 4:1 to 1:4.